EP0021868B1 - Process for the preparation of diaryl ethers - Google Patents
Process for the preparation of diaryl ethers Download PDFInfo
- Publication number
- EP0021868B1 EP0021868B1 EP80400595A EP80400595A EP0021868B1 EP 0021868 B1 EP0021868 B1 EP 0021868B1 EP 80400595 A EP80400595 A EP 80400595A EP 80400595 A EP80400595 A EP 80400595A EP 0021868 B1 EP0021868 B1 EP 0021868B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- amine
- tris
- formula
- reaction
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000001987 diarylethers Chemical class 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000003352 sequestering agent Substances 0.000 claims abstract description 28
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 32
- -1 alkali metal phenolate Chemical class 0.000 claims description 31
- 150000003254 radicals Chemical class 0.000 claims description 29
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 27
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 27
- 229940045803 cuprous chloride Drugs 0.000 claims description 27
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 16
- 239000005749 Copper compound Substances 0.000 claims description 13
- 150000001880 copper compounds Chemical class 0.000 claims description 13
- 229940031826 phenolate Drugs 0.000 claims description 13
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 12
- UDONPJKEOAWFGI-UHFFFAOYSA-N 1-methyl-3-phenoxybenzene Chemical compound CC1=CC=CC(OC=2C=CC=CC=2)=C1 UDONPJKEOAWFGI-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XGLVDUUYFKXKPL-UHFFFAOYSA-N 2-(2-methoxyethoxy)-n,n-bis[2-(2-methoxyethoxy)ethyl]ethanamine Chemical compound COCCOCCN(CCOCCOC)CCOCCOC XGLVDUUYFKXKPL-UHFFFAOYSA-N 0.000 claims description 8
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 8
- XZGIHWAIIZHXKX-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-n,n-bis[2-(2-ethoxyethoxy)ethyl]ethanamine Chemical compound CCOCCOCCN(CCOCCOCC)CCOCCOCC XZGIHWAIIZHXKX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 claims description 5
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 claims description 4
- WBUOVKBZJOIOAE-UHFFFAOYSA-N 3-chlorobenzonitrile Chemical compound ClC1=CC=CC(C#N)=C1 WBUOVKBZJOIOAE-UHFFFAOYSA-N 0.000 claims description 3
- MRLGCTNJRREZHZ-UHFFFAOYSA-N 3-phenoxybenzaldehyde Chemical compound O=CC1=CC=CC(OC=2C=CC=CC=2)=C1 MRLGCTNJRREZHZ-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000003738 xylenes Chemical class 0.000 claims description 2
- HPRCCXIECBBMPJ-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]-n,n-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]ethanamine Chemical compound COCCOCCOCCN(CCOCCOCCOC)CCOCCOCCOC HPRCCXIECBBMPJ-UHFFFAOYSA-N 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 abstract description 5
- 150000004707 phenolate Chemical class 0.000 abstract description 4
- 150000001502 aryl halides Chemical class 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 description 67
- 239000007983 Tris buffer Substances 0.000 description 62
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 32
- 238000010992 reflux Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 18
- 125000004429 atom Chemical group 0.000 description 15
- 150000005171 halobenzenes Chemical class 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 0 *c1ccc(C2CCCCC2)cc1 Chemical compound *c1ccc(C2CCCCC2)cc1 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- IBUQEIIFTPFARK-UHFFFAOYSA-N 3-phenoxybenzonitrile Chemical compound N#CC1=CC=CC(OC=2C=CC=CC=2)=C1 IBUQEIIFTPFARK-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- FIIZQHKGJMRJIL-UHFFFAOYSA-N n,3-diphenylprop-2-enamide Chemical compound C=1C=CC=CC=1C=CC(=O)NC1=CC=CC=C1 FIIZQHKGJMRJIL-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 3
- FIPTYOFKSOWKTF-UHFFFAOYSA-N 1,2-diphenoxybenzene Chemical compound C=1C=CC=C(OC=2C=CC=CC=2)C=1OC1=CC=CC=C1 FIPTYOFKSOWKTF-UHFFFAOYSA-N 0.000 description 2
- ZCJAYDKWZAWMPR-UHFFFAOYSA-N 1-chloro-2-fluorobenzene Chemical compound FC1=CC=CC=C1Cl ZCJAYDKWZAWMPR-UHFFFAOYSA-N 0.000 description 2
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- WCOYPFBMFKXWBM-UHFFFAOYSA-N 1-methyl-2-phenoxybenzene Chemical compound CC1=CC=CC=C1OC1=CC=CC=C1 WCOYPFBMFKXWBM-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- HCJMNOSIAGSZBM-UHFFFAOYSA-N 6-methylsalicylic acid Chemical compound CC1=CC=CC(O)=C1C(O)=O HCJMNOSIAGSZBM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical class Cl* 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-M naphthalen-1-olate Chemical compound C1=CC=C2C([O-])=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-M 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- ONFAAMBUOAGWSG-UHFFFAOYSA-M sodium;2-methylphenolate Chemical compound [Na+].CC1=CC=CC=C1[O-] ONFAAMBUOAGWSG-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- MGAXYKDBRBNWKT-UHFFFAOYSA-N (5-oxooxolan-2-yl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1OC(=O)CC1 MGAXYKDBRBNWKT-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- IPBRZLMGGXHHMS-UHFFFAOYSA-N 1-chloro-2-phenoxybenzene Chemical compound ClC1=CC=CC=C1OC1=CC=CC=C1 IPBRZLMGGXHHMS-UHFFFAOYSA-N 0.000 description 1
- CQEJHAZKRXIMDK-UHFFFAOYSA-N 1-fluoro-3-methyl-2-phenoxybenzene Chemical compound CC1=CC=CC(F)=C1OC1=CC=CC=C1 CQEJHAZKRXIMDK-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- GCRPYRGGTDLAOS-UHFFFAOYSA-N 2-[bis(1-hydroxypropan-2-yl)amino]propan-1-ol Chemical compound OCC(C)N(C(C)CO)C(C)CO GCRPYRGGTDLAOS-UHFFFAOYSA-N 0.000 description 1
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OQMROCZLIQULED-UHFFFAOYSA-N CC(C1)=CC([CH2+])=CC1=C Chemical compound CC(C1)=CC([CH2+])=CC1=C OQMROCZLIQULED-UHFFFAOYSA-N 0.000 description 1
- IEALXHQYEVTYMO-UHFFFAOYSA-N CC(CCC=C1)C1O Chemical compound CC(CCC=C1)C1O IEALXHQYEVTYMO-UHFFFAOYSA-N 0.000 description 1
- FAVXLBFTFRKECO-UHFFFAOYSA-N CC1=CC=CC(C1)(OC2=CC=CC=C2)F Chemical compound CC1=CC=CC(C1)(OC2=CC=CC=C2)F FAVXLBFTFRKECO-UHFFFAOYSA-N 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N COC1CCCCC1 Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N Cc(cccc1)c1O Chemical compound Cc(cccc1)c1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- GWHJZXXIDMPWGX-UHFFFAOYSA-N Cc1ccc(C)c(C)c1 Chemical compound Cc1ccc(C)c(C)c1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- SLHSZNQIHNFAGY-UHFFFAOYSA-M potassium;2-hydroxy-6-methylbenzoate Chemical compound [K+].CC1=CC=CC(O)=C1C([O-])=O SLHSZNQIHNFAGY-UHFFFAOYSA-M 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- BVUAIIPVLGTEMU-UHFFFAOYSA-N sodium;2-ethoxyethanolate Chemical compound [Na+].CCOCC[O-] BVUAIIPVLGTEMU-UHFFFAOYSA-N 0.000 description 1
- UIICPZFWHBJNIG-UHFFFAOYSA-N sodium;2-methoxyethanolate Chemical compound [Na+].COCC[O-] UIICPZFWHBJNIG-UHFFFAOYSA-N 0.000 description 1
- WHQZPTTYEYXMIZ-UHFFFAOYSA-M sodium;3-hydroxy-2-methylbenzoate Chemical compound [Na+].CC1=C(O)C=CC=C1C([O-])=O WHQZPTTYEYXMIZ-UHFFFAOYSA-M 0.000 description 1
- QOINKMNRLBCJOP-UHFFFAOYSA-M sodium;3-methylphenolate Chemical compound [Na+].CC1=CC=CC([O-])=C1 QOINKMNRLBCJOP-UHFFFAOYSA-M 0.000 description 1
- QXGDIAJDPHVEBJ-UHFFFAOYSA-N sodium;heptan-1-olate Chemical compound [Na+].CCCCCCC[O-] QXGDIAJDPHVEBJ-UHFFFAOYSA-N 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
Definitions
- the present invention relates to a process for the preparation of diaryl ethers; by reaction of an unactivated halobenzene and a phenolate or naphtholate in the presence of a copper compound.
- phenolate will be used to denote either a phenolate or a naphtholate.
- the present invention therefore relates to a process for the preparation of diaryl ether by reaction of an unactivated halobenzene and an alkaline phenolate in the presence of a copper compound, characterized in that the reaction takes place in the presence of at least one sequestering agent of formula: in which n is an integer greater than or equal to 0 and less than or equal to approximately 10 (0 _ n, 10), R 1 ' R 2 , R 3 and R 4 identical or different represent a hydrogen atom or a radical alkyl having from 1 to 4 carbon atoms and R 5 represents an alkyl or cycloalkyl radical having from 1 to 12 carbon atoms, a phenyl radical or a radical -C m H 2m - ⁇ or C m H 2m + 1 - ⁇ - , where m is between 1 and 12 (1 ⁇ m - 12).
- the copper compound complexed by the sequestering agent, the phenolate complexed by the sequestering agent and the halobenzene are soluble in the solvent considered, the sequestering agent being soluble in this same solvent.
- the sequestering agent is used in an amount such that the molar ratio of the copper compound to the sequestering agent of formula I is preferably between approximately 0.05 and 10. Even more preferably, this ratio is between approximately 0.1 and 5.
- the molar ratio of halobenzene to phenolate is preferably between approximately 0.8 and approximately 50. More preferably, this ratio is between approximately 0.9 and approximately 30. The high values of this ratio correspond to the case where the halobenzene also serves as a solvent.
- the procedure is as in b) without adding tris (dioxa-3,6 octyl) amine.
- the transformation rate after 6 h is 15%.
- the salts formed are extracted with acidic water and then the organic mass is subjected to a distillation in order to remove the excess of chlorobenzene, the unreacted cresol, then the m - phenoxytoluene. Thereby obtaining 21.6 kg of m-phenoxytoluene, or a yield of 8 9%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
La présente invention a pour objet un procédé de préparation d'éthers diaryliques ; par réaction d'un halogénobenzène non activé et d'un phénolate ou naphtolate en présence d'un composé du cuivre. Dans la suite de la description et des revendications, on utilisera le terme « phénolate » pour désigner soit un phénolate soit un naphtolate.The present invention relates to a process for the preparation of diaryl ethers; by reaction of an unactivated halobenzene and a phenolate or naphtholate in the presence of a copper compound. In the following description and claims, the term "phenolate" will be used to denote either a phenolate or a naphtholate.
Cette réaction est bien connue dans l'art antérieur : c'est la synthèse d'Ullmann des éthers mettant en oeuvre, en présence d'un composé du cuivre comme catalyseur, un halogénobenzène non activé (c'est-à-dire ne comportant pas ortho ou para du groupement halogeno un groupement activant sélectivement les positions ortho et para) avec un phénolate.This reaction is well known in the prior art: it is the Ullmann synthesis of ethers using, in the presence of a copper compound as catalyst, an unactivated halobenzene (that is to say having no not ortho or para of the halogeno group a group selectively activating the ortho and para) positions with a phenolate.
Plus précisément, on connaît le brevet britannique n° 1 052 390 qui décrit la réaction du m-crésolate de potassium et du bromobenzène en présence de bronze de cuivre activé pour obtenir le phénoxy-3 toluène. Cette réaction a lieu dans le bromobenzène à 220 °C-240 °C. Le principal inconvénient de ce type de procédé est qu'il fait intervenir le dérivé bromé en grande quantité, ce dernier étant utilisé à la fois comme réactif et comme solvant. Or, l'homme de l'art sait bien que le dérivé bromé est onéreux. Un autre inconvénient majeur réside dans la température élevée à laquelle a lieu la réaction.More specifically, British Patent No. 1,052,390 is known, which describes the reaction of potassium m-cresolate and bromobenzene in the presence of activated copper bronze to obtain 3-phenoxy-toluene. This reaction takes place in bromobenzene at 220 ° C-240 ° C. The main drawback of this type of process is that it involves the brominated derivative in large quantities, the latter being used both as a reagent and as a solvent. However, those skilled in the art are well aware that the brominated derivative is expensive. Another major drawback is the high temperature at which the reaction takes place.
Il existe cependant des procédés qui permettent l'utilisation du dérivé chloré. On connaît en particulier la demande de brevet japonais 72/104672 qui décrit un procédé de préparation de metaphénoxytoluène selon lequel on fait réagir un sel alcalin de métacrésol avec du chlorobenzène en présence de bases organiques, en utilisant de la poudre de cuivre ou des composés du cuivre comme catalyseur. La réaction a lieu dans la quinoléine à des températures de l'ordre de 200 °C. Le gros inconvénient de ce procédé, quand est envisagée son application à l'échelle industrielle, est sans aucun doute le fait qu'un solvant comme la quinoléine présente de nombreux désavantages qui tiennent à sa difficulté de mise en oeuvre et à son prix.However, there are methods which allow the use of the chlorinated derivative. Japanese patent application 72/104672 is known in particular, which describes a process for the preparation of metaphenoxytoluene according to which an alkali salt of metacresol is reacted with chlorobenzene in the presence of organic bases, using copper powder or compounds of copper as a catalyst. The reaction takes place in quinoline at temperatures of the order of 200 ° C. The big drawback of this process, when considering its application on an industrial scale, is undoubtedly the fact that a solvent such as quinoline has many disadvantages due to its difficulty of implementation and its price.
Une autre demande de brevet japonais, la demande 77/035128 décrit un procédé permettant la réaction du chlorobenzène et du m-crésolate en présence du cuivre ou de composés du cuivre sans utiliser de solvant.Another Japanese patent application, application 77/035128 describes a process allowing the reaction of chlorobenzene and m-cresolate in the presence of copper or copper compounds without using a solvent.
La mise en oeuvre de ce procédé à l'échelle industrielle soulève de très gros problèmes puisqu'il est nécessaire de travailler sous pression et à des températures élevées (200-250 °C).The implementation of this process on an industrial scale raises very big problems since it is necessary to work under pressure and at high temperatures (200-250 ° C).
On constate donc que dans le cadre d'un procédé de préparation d'éthers diaryliques par réaction d'un halogénobenzène non activé et d'un phénolate en présence d'un composé du cuivre, l'art antérieur ne permet pas une mise en oeuvre industrielle aisée et générale de la réaction d'Ullmann. Les besoins non satisfaits par l'art antérieur peuvent s'analyser en trois points pris isolément ou en combinaison. Le premier concerne le solvant : il serait souhaitable de pouvoir utiliser industriellement des solvants ayant une faible toxicité ainsi qu'une bonne stabilité thermique et chimique tout en n'obérant pas l'économie du procédé ; il serait en particulier avantageux dans de nombreux cas de pouvoir utiliser un des réactifs comme solvant. Le second point concerne la température de réaction : il est clair que l'abaissement de la température de réaction serait un avantage très appréciable à la fois au plan technique et au plan économique. Il faut en particulier souligner la nécessité qu'il y a à opérer à des températures les plus basses possibles lorsque les réactifs ou les produits obtenus sont sensibles aux effets thermiques. Le troisième point concerne l'halogénobenzène : comme cela ressort de ce qui précède, il serait souhaitable de remplacer les dérivés bromés par les dérivés chlorés correspondants dans des conditions de réaction semblables.It can therefore be seen that in the context of a process for the preparation of diaryl ethers by reaction of an inactivated halobenzene and a phenolate in the presence of a copper compound, the prior art does not allow an implementation easy and general industrial reaction of Ullmann. The needs not satisfied by the prior art can be analyzed in three points taken individually or in combination. The first concerns the solvent: it would be desirable to be able to use solvents industrially having a low toxicity as well as good thermal and chemical stability while not affecting the economy of the process; it would be particularly advantageous in many cases to be able to use one of the reactants as solvent. The second point concerns the reaction temperature: it is clear that lowering the reaction temperature would be a very appreciable advantage both technically and economically. In particular, it is necessary to stress the necessity of operating at the lowest possible temperatures when the reagents or the products obtained are sensitive to thermal effects. The third point concerns halobenzene: as is apparent from the above, it would be desirable to replace the brominated derivatives with the corresponding chlorinated derivatives under similar reaction conditions.
Les travaux de la demanderesse ont conduit à un procédé de préparation d'éthers diaryliques qui satisfait ces besoins.The work of the applicant has led to a process for the preparation of diaryl ethers which satisfies these needs.
La présente invention a donc pour objet un procédé de préparation d'éther diarylique par réaction d'un halogénobenzène non activé et d'un phénolate alcalin en présence d'un composé du cuivre, caractérisé en ce que la réaction a lieu en présence d'au moins un agent séquestrant de formule :
La réaction peut avoir lieu en l'absence ou en présence de solvant.The reaction can take place in the absence or presence of a solvent.
L'invention repose sur le fait que l'agent sequestrant de formule (I) forme d'une part avec le composé du cuivre et d'autre part avec le phénolate alcalin des complexes qui sont solubles dans le milieu réactionnel alors que le composé du cuivre et le phénolate sont à l'état non complexé insolubles ou très peu solubles dans ledit milieu. Cette complexation a un double effet : en premier lieu, elle permet la solubilisation du catalyseur et du phénolate et de ce fait permet à la réaction d'avoir lieu ; en second lieu, bien que cela ne soit pas complètement expliqué, il semble que la complexation active le système réactionnel de telle sorte que la réaction a lieu dans des conditions beaucoup plus douces que celles de l'art antérieur. C'est ainsi qu'on opère à des températures relativement basses et sous pression atmosphérique tout en utilisant le dérivé chloré. Il est bien entendu que l'invention s'applique de la même façon aux autres halogénobenzènes comme les bromobenzènes par exemple bien que dans ce cas l'intérêt industriel soit dans la majorité des cas moins marqué.The invention is based on the fact that the sequestering agent of formula (I) forms on the one hand with the copper compound and on the other hand with the alkaline phenolate complexes which are soluble in the reaction medium while the compound of copper and the phenolate are in the uncomplexed state insoluble or very slightly soluble in said medium. This complexation has a double effect: firstly, it allows the solubilization of the catalyst and of the phenolate and therefore allows the reaction to take place; secondly, although this is not fully explained, it seems that the complexation activates the reaction system so that the reaction takes place under much milder conditions than those of the prior art. This is how we operate at relatively low temperatures and under pressure atmospheric while using the chlorine derivative. It is understood that the invention applies in the same way to other halobenzenes such as bromobenzenes for example although in this case the industrial interest is in the majority of cases less marked.
Lorsqu'on opère sans solvant, le composé du cuivre complexé par l'agent séquestrant et le phénolate alcalin complexé par le même agent séquestrant sont solubles dans l'halogénobenzène, l'agent séquestrant étant soluble dans l'halogénobenzène.When operating without solvent, the copper compound complexed by the sequestering agent and the alkaline phenolate complexed by the same sequestering agent are soluble in halobenzene, the sequestering agent being soluble in halobenzene.
Lorsqu'on opère en présence de solvant, le composé du cuivre complexé par l'agent séquestrant, le phénolate complexé par l'agent séquestrant et l'halogénobenzène sont solubles dans le solvant considéré, l'agent séquestrant étant soluble dans ce même solvant.When operating in the presence of a solvent, the copper compound complexed by the sequestering agent, the phenolate complexed by the sequestering agent and the halobenzene are soluble in the solvent considered, the sequestering agent being soluble in this same solvent.
Selon un mode de réalisation préférentiel de l'invention, on utilise un agent séquestrant de formule (I) dans laquelle R1, R2, R3 et R4 représentent un atome d'hydrogène ou un radical méthyle, Rs et n ayant la signification précédente.According to a preferred embodiment of the invention, a sequestering agent of formula (I) is used in which R 1 , R 2 , R 3 and R 4 represent a hydrogen atom or a methyl radical, R s and n having the previous meaning.
Parmi ces derniers, on préfère encore plus particulièrement mettre en oeuvre les agents séquestrants pour lesquels n est supérieur ou égal à 0 et inférieur ou égal à 6 et pour lesquels R5 représente un radical alkyle ayant de 1 à 4 atomes de carbone.Among the latter, it is still more particularly preferred to use the sequestering agents for which n is greater than or equal to 0 and less than or equal to 6 and for which R 5 represents an alkyl radical having from 1 to 4 carbon atoms.
On peut citer :
- - la tris(oxa-3 butyl)amine de formule :
- - la tris(dioxa-3,6 heptyl)amine de formule :
- - la tris(trioxa-3,6,9 décyl)amine de formule :
- - la tris(dioxa-3,6 octyl)amine de formule :
- - la tris(trioxa-3,6,9 undécyl)amine de formule :
- - la tris(dioxa-3,6 nonyl)amine de formule :
- - la tris(trioxa-3,6,9 dodécyl)amine de formule :
- - la tris(dioxa-3,6 décyl)amine de formule :
- - la tris(trioxa-3,6,9 tridécyi)amine de formule :
- - la tris(tetra-oxa-3,6,9,12 tridecyl)amine de formule :
- - la tris(hexa-oxa-3,6,9,12,15,18 nonadecyl)amine de formule
- - la tris(dioxa-3,6 méthyl-4 heptyl)amine de formule :
- - la tris(dioxa-3,6 diméthyl-2,4 heptyl)amine de formule :
- - Tris (3-oxa-butyl) amine of formula:
- - tris (dioxa-3,6 heptyl) amine of formula:
- - the tris (trioxa-3,6,9 decyl) amine of formula:
- - the tris (dioxa-3,6 octyl) amine of formula:
- - the tris (trioxa-3,6,9 undecyl) amine of formula:
- - Tris (dioxa-3,6 nonyl) amine of formula:
- - the tris (trioxa-3,6,9 dodecyl) amine of formula:
- - the tris (dioxa-3,6 decyl) amine of formula:
- - the tris (trioxa-3,6,9 tridécyi) amine of formula:
- - the tris (tetra-oxa-3,6,9,12 tridecyl) amine of formula:
- - the tris (hexa-oxa-3,6,9,12,15,18 nonadecyl) amine of formula
- - Tris (3,6-dioxa-4-methyl-heptyl) amine of formula:
- - Tris (3,6-dioxa-2,4-dimethyl-heptyl) amine of formula:
Les amines utilisées dans le procédé selon l'invention sont connues en tant que telles dans l'art antérieur. C'est ainsi que le brevet français 1 302 365 cite l'obtention des amines tertiaires N-(CH2-CH2-O-CH3)3 et N-(CH2-CH2-O-CH2-CH2-O-CH3)3 comme sous produits de la synthèse des amines primaires et secondaires correspondantes, ces amines primaires et secondaires étant des produits intéressants comme intermédiaires en vue de la synthèse de substances pharmaceutiques, comme inhibiteurs de corrosion comme intermédiaires en vue de la synthèse de produits chimiques intéressants en agriculture et comme émulsifiants.The amines used in the process according to the invention are known as such in the prior art. French patent 1,302,365 cites the production of tertiary amines N- (CH 2 -CH 2 -O-CH 3 ) 3 and N- (CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 3 ) 3 as by-products of the synthesis of the corresponding primary and secondary amines, these primary and secondary amines being products of interest as intermediates for the synthesis of pharmaceutical substances, as corrosion inhibitors as intermediates for the synthesis of chemicals of interest in agriculture and as emulsifiers.
Le procédé selon l'invention est applicable à la réaction d'un halogénobenzène de formule générale :
- n est supérieur ou égal à 1 et inférieur ou égal à 6 (1 ≤ n ≤ 6).
- le ou les radicaux X identiques ou différents sont choisis parmi le groupe comprenant CI, Br et I.
- le ou les radicaux R6 identiques ou différents sont choisis parmi le groupe comprenant :
- - l'hydrogène
- - les radicaux alkyle et cycloalkyle ayant de 1 à 12 atomes de carbone
- - les radicaux alcényle ayant de 3 à 12 atomes de carbone comme les radicaux propényle, nonyle, dodécyle, par exemple
- - les radicaux de formules CmH2m+1-Ø- , CmH2m 1-Ø-; et Ø-CmH2m- où m est un nombre entier compris entre 1 et 12 (1 ≤ m ≤ 12) et où Ø peut être substitué
- - les radicaux alkoxy ayant de 1 à 12 atomes de carbone et les radicaux phénoxy
- - les radicaux -CmH2m-OH et -CmH2m OR où m est un nombre entier compris entre 1 et 12 (1 ≤ m ≤ 12) et où R est un radical alkyle ayant de 1 à 12 atomes de carbone ou un radical phényle.
- - les radicaux alkylthio ayant de 1 à 12 atomes de carbone et les radicaux phénylthio
- - les radicaux CpH2p 1 q Fq, p étant compris entre 1 et 4 (1 ≤ p ≤ 4) et q étant compris entre 3 et 9 (3 ≤ q ≤ 9) comme --CF3 et -CH2-CF3 par exemple
- - les radicaux
- - et les radicaux -NO2, -S03M, -CN, -C02M, -C02R. -COR, -COH où M représente un métal alcalin et où R représente un radical alkyle ayant de 1 à 12 atomes de carbone ou un radical phényle.
- n is greater than or equal to 1 and less than or equal to 6 (1 ≤ n ≤ 6).
- the identical or different radicals X are chosen from the group comprising CI, Br and I.
- the identical or different radicals R 6 are chosen from the group comprising:
- - hydrogen
- - alkyl and cycloalkyl radicals having from 1 to 12 carbon atoms
- - alkenyl radicals having 3 to 12 carbon atoms such as propenyl, nonyl, dodecyl radicals, for example
- - the radicals of formulas C m H 2m + 1 -Ø-, C m H 2m 1 -Ø-; and Ø-C m H 2m - where m is an integer between 1 and 12 (1 ≤ m ≤ 12) and where Ø can be substituted
- - alkoxy radicals having from 1 to 12 carbon atoms and phenoxy radicals
- - the radicals -C m H 2m -OH and -C m H 2m OR where m is an integer between 1 and 12 (1 ≤ m ≤ 12) and where R is an alkyl radical having from 1 to 12 carbon atoms or a phenyl radical.
- - alkylthio radicals having from 1 to 12 carbon atoms and phenylthio radicals
- - the radicals C p H 2p 1 q Fq, p being between 1 and 4 (1 ≤ p ≤ 4) and q being between 3 and 9 (3 ≤ q ≤ 9) as --CF 3 and -CH2-CF3 for example
- - radicals
- - and the radicals -NO 2 , -S0 3 M, -CN, -C0 2 M, -C0 2 R. -COR, -COH where M represents an alkali metal and where R represents an alkyl radical having from 1 to 12 atoms of carbon or a phenyl radical.
Lorsque R6 est en position ortho ou para d'un substituant X il ne peut représenter l'un des radicaux -NO2, -S03M, -CN, -C02M, -C02R, -COR et -S02R définis ci-dessus, ces radicaux activant en effet sélectivement ces positions ortho et para.When R 6 is in the ortho or para position of a substituent X it cannot represent one of the radicals -NO 2 , -S0 3 M, -CN, -C0 2 M, -C0 2 R, -COR and -S0 2 R defined above, these radicals selectively activating these ortho and para positions.
Les phénolates pouvant être mis en œuvre selon le procédé de l'invention ont pour formule :
- Ar représente un radical phényle ou naphtyle éventuellement substitué
- M' représente un cation choisi parmi le groupe comprenant les cations dérivés des métaux alcalins et r est un nombre entier compris entre 1 et 3 (1 ≤ r ≤ 3)
- Ar represents an optionally substituted phenyl or naphthyl radical
- M 'represents a cation chosen from the group comprising cations derived from alkali metals and r is an integer between 1 and 3 (1 ≤ r ≤ 3)
Plus particulièrement, l'invention concerne les composés de formules :
- r est égal à 1 ou 2
- le ou les cations M+, identiques ou différents, sont choisis parmi le groupe comprenant Li+, Na+, K+.
- le ou les radicaux R7, identiques ou différents, sont choisis parmi le groupe comprenant :
- - l'hydrogène
- - les radicaux alkyle et cycloalkyle ayant de 1 à 12 atomes de carbone
- - les radicaux alcényle ayant de 3 à 12 atomes de carbone comme les radicaux propényle, nonyle, dodécyle, par exemple
- - les radicaux de formules CmH2m+1Ø-; CmH2m-1Ø- ; et Ø-CmH2m- où m est un nombre entier compris entre 1 et 12 (1≤m≤12) et où Ø peut être substitué
- - les radicaux alkoxy ayant de 1 à 12 atomes de carbone et les radicaux phénoxy
- - les radicaux -CmH2m -OH et -CmH2m OR où m est un nombre entier compris entre 0 et 12 (0≤m≤12) et où R est un radical alkyle ayant de 1 à 12 atomes de carbone ou un radical phényle
- - les radicaux alkylthio ayant de 1 à 12 atomes de carbone et les radicaux phénylthio
- - les radicaux CpH2p+1-1Fq, p étant compris entre 1 et 4 (1≤p≤4) et q étant compris entre 3 et 9 (3≤q≤9) comme -CF3 et -CH2-CF3 par exemple
- - les radicaux
- - les radicaux CI et F
- - et les radicaux -N02, NH2, NHR, NRR, -SO3M, -CN, -CO2M, -CO2R, -COR, -COH, -S02R où M représente un métal alcalin et où R représente un radical alkyle ayant de 1 à 12 atomes de carbone ou un radical phényle.
- r is 1 or 2
- the identical or different M + cation (s) are chosen from the group comprising Li + , Na + , K +.
- the radical or radicals R 7 , which are identical or different, are chosen from the group comprising:
- - hydrogen
- - alkyl and cycloalkyl radicals having from 1 to 12 carbon atoms
- - alkenyl radicals having 3 to 12 carbon atoms such as propenyl, nonyl, dodecyl radicals, for example
- - radicals of formulas C m H 2m + 1 Ø-; C m H 2m-1 Ø-; and Ø-C m H 2m - where m is an integer between 1 and 12 (1≤m≤12) and where Ø can be substituted
- - alkoxy radicals having from 1 to 12 carbon atoms and phenoxy radicals
- - the radicals -C m H 2m -OH and -C m H 2m OR where m is an integer between 0 and 12 (0≤m≤12) and where R is an alkyl radical having from 1 to 12 carbon atoms or a phenyl radical
- - alkylthio radicals having from 1 to 12 carbon atoms and phenylthio radicals
- - the radicals C p H 2p + 1-1 F q , p being between 1 and 4 (1≤p≤4) and q being between 3 and 9 (3≤q≤9) as -CF 3 and -CH 2 -CF 3 for example
- - radicals
- - the radicals CI and F
- - and the radicals -N0 2 , NH 2 , NHR, NRR, -SO 3 M, -CN, -CO 2 M, -CO 2 R, -COR, -COH, -S0 2 R where M represents an alkali metal and where R represents an alkyl radical having from 1 to 12 carbon atoms or a phenyl radical.
L'invention vise plus particulièrement, mais non exclusivement, la réaction d'un composé de formule II ne contenant qu'un substituant X avec un composé de formule III ne contenant qu'un substituant 0-M+ ainsi que la réaction d'un composé de formule Il contenant un substituant X avec un composé de formule III contenant plusieurs substituants O-M+ et inversement c'est-à-dire un composé de formule Il contenant plusieurs substituants X avec un composé de formule III contenant un substituant O-M+. The invention relates more particularly, but not exclusively, to the reaction of a compound of formula II containing only one substituent X with a compound of formula III containing only one substituent O-M + as well as the reaction of a compound of formula II containing a substituent X with a compound of formula III containing several substituents OM + and conversely, that is to say a compound of formula II containing several substituents X with a compound of formula III containing a substituent OM +.
On peut citer comme exemples d'halogénobenzènes de formule II les composés suivants :
On peut citer comme exemples de phénolates de formules Illa et Illb les composés dérivés des phénols et naphtols suivants :
Le choix de l'agent séquestrant le plus adapté à la mise en oeuvre du procédé selon l'invention doit être fait en tenant compte de la taille du cation M+. Plus la taille du cation sera importante, plus le nombre d'atomes d'oxygène contenus dans la molécule de l'agent séquestrant devra être élevé. C'est ainsi que si on utilise un phénolate de potassium on préférera utiliser la tris(trioxa-3,6,9 décyl)amine alors qu'avec le sel de sodium correspondant la tris(dioxa-3,6 heptyl)amine sera préférée.The choice of the sequestering agent most suited to the implementation of the method according to the invention must be made taking into account the size of the cation M +. The larger the size of the cation, the higher the number of oxygen atoms contained in the sequestering agent molecule. Thus if we use a potassium phenolate we will prefer to use the tris (trioxa-3,6,9 decyl) amine while with the corresponding sodium salt the tris (dioxa-3,6 heptyl) amine will be preferred .
Le solvant, lorsqu'on en utilise un, doit répondre à un certain nombre de conditions : il faut d'abord qu'il solubilise l'agent séquestrant (ce dernier est soluble dans la plupart des solvants usuels) ; il faut aussi qu'il soit inerte chimiquement vis-à-vis des sels à dissoudre. Il faut aussi noter que pour obtenir la meilleure mise en oeuvre du procédé selon l'invention, plus le solvant choisi aura un caractère apolaire marqué, plus l'agent séquestrant devra avoir un caractère lipophile marqué (c'est-à-dire plus l'agent séquestrant devra contenir d'atomes de carbone).The solvent, when one is used, must meet a certain number of conditions: it must first of all dissolve the sequestering agent (the latter is soluble in most of the usual solvents); it must also be chemically inert with respect to the salts to be dissolved. It should also be noted that in order to obtain the best implementation of the method according to the invention, the more the solvent chosen will have a marked apolar character, the more the sequestering agent will have to have a marked lipophilic character (that is to say the sequestering agent must contain carbon atoms).
On peut, par exemple utiliser comme solvant :
- l'oxyde de diphényle, l'anisole, le toluène, les polyéthers de glycol, le benzène, les xylènes.
- diphenyl oxide, anisole, toluene, polyethers of glycol, benzene, xylenes.
Les composés du cuivre utilisables comme catalyseurs sont connus dans l'art antérieur. On peut citer : Cu CI, Cu Br, Cu l, Cu O COCH3, CU20. Selon un mode de mise en oeuvre préféré, on utilise Cu CI ou Cu Br.Copper compounds which can be used as catalysts are known in the prior art. Mention may be made of: Cu CI, Cu Br, Cu l, Cu O COCH 3 , C U2 0. According to a preferred embodiment, Cu CI or Cu Br is used.
Le procédé selon l'invention est mis en oeuvre à une température comprise entre 50 °C et 200 °C environ. D'une façon préférentielle, on opère à une température comprise entre environ 100 et environ 180 °C.The process according to the invention is carried out at a temperature of between 50 ° C and 200 ° C approximately. Preferably, the operation is carried out at a temperature between approximately 100 and approximately 180 ° C.
Comme cela a été dit plus haut, on opère généralement à la pression atmosphérique. Bien entendu, les pressions inférieures ou supérieures à la pression atmosphérique ne sont pas exclues par la présente invention.As said above, it is generally carried out at atmospheric pressure. Of course, pressures below or above atmospheric pressure are not excluded by the present invention.
On utilise l'agent séquestrant en quantité telle que le rapport molaire du composé du cuivre à l'agent séquestrant de formule I est de préférence compris entre environ 0,05 et 10. Encore plus préférentiellement, ce rapport est compris entre environ 0,1 et 5.The sequestering agent is used in an amount such that the molar ratio of the copper compound to the sequestering agent of formula I is preferably between approximately 0.05 and 10. Even more preferably, this ratio is between approximately 0.1 and 5.
Le rapport molaire du composé du cuivre au phénolate est de préférence compris entre environ 0,005 et environ 0,15. Il est encore plus préférentiellement compris entre 0,01 et 0,1 environ.The molar ratio of the copper compound to the phenolate is preferably between about 0.005 and about 0.15. It is even more preferably between 0.01 and 0.1 approximately.
Le rapport molaire de l'halogénobenzène au phénolate est compris de préférence entre environ 0,8 et environ 50. Plus préférentiellement, ce rapport est compris entre 0,9 environ et 30 environ. Les hautes valeurs de ce rapport correspondent au cas où l'halogénobenzène sert aussi de solvant.The molar ratio of halobenzene to phenolate is preferably between approximately 0.8 and approximately 50. More preferably, this ratio is between approximately 0.9 and approximately 30. The high values of this ratio correspond to the case where the halobenzene also serves as a solvent.
Les composés obtenus selon la présente invention ont les formules générales IV suivantes :The compounds obtained according to the present invention have the following general formulas IV:
On peut citer comme exemples de composés de formule IV, les composés suivants :
Ils sont utiles notamment comme intermédiaires pour la synthèse de composés ayant une activité phytosanitaire et pharmaceutique.They are useful in particular as intermediates for the synthesis of compounds having phytosanitary and pharmaceutical activity.
Les agents séquestrants de formule I utilisés dans le procédé selon l'invention peuvent être préparés par condensation d'un sel de formule :
Le rapport molaire sel de métal alcalin/amine est compris entre environ 3 et environ 5.The alkali metal salt / amine molar ratio is between approximately 3 and approximately 5.
L'opération de condensation est réalisée à une température comprise entre 100 et 150 °C pendant 1 à 15 h en présence d'un solvant qui peut être par exemple le chlorobenzène ou de préférence le monoalkyléther d'éthylène glycol de formule R5-(O-CHR4-CHR3)n-OH.The condensation operation is carried out at a temperature between 100 and 150 ° C for 1 to 15 h in the presence of a solvent which may be, for example, chlorobenzene or preferably the monoalkylether of ethylene glycol of formula R 5 - ( O-CHR 4 -CHR 3 ) n -OH.
On opère de préférence de telle sorte qu'on ait une solution contenant de 2 à 5 moles de sel de métal alcalin par litre de solvant.It is preferably carried out in such a way that there is a solution containing from 2 to 5 moles of alkali metal salt per liter of solvent.
Le mélange en fin de réaction contient principalement l'amine tertiaire de formule :
Les amines tertiaires, secondaires et primaires sont généralement respectivement dans le rapport 90 : 8 : 2 après distillation.Tertiary, secondary and primary amines are generally in the ratio 90: 8: 2 respectively after distillation.
On peut utiliser dans le procédé selon l'invention directement le mélange ci-dessus obtenu après première distillation, c'est-à-dire contenant les trois types d'amines.Can be used in the process according to the invention directly the above mixture obtained after first distillation, that is to say containing the three types of amines.
On préfère pour une meilleure mise en oeuvre de l'invention effectuer une distillation plus poussée du mélange ci-dessus afin d'obtenir une amine tertiaire sensiblement pure.It is preferred for a better implementation of the invention to carry out a further distillation of the above mixture in order to obtain a substantially pure tertiary amine.
D'autres caractéristiques et avantages de l'invention apparaîtront plus clairement à la lecture des exemples qui vont suivre. Ces exemples ne sauraient en aucune manière être considérés comme une limitation de l'invention.Other characteristics and advantages of the invention will appear more clearly on reading the examples which follow. These examples should in no way be considered as a limitation of the invention.
Préparation du métaphénoxytoluène
Dans un ballon tricol de 2 I équipé d'une agitation, d'un thermomètre, d'une ampoule de coulée et d'un séparateur de fraction, on charge 216 g (2 moles) de métacrésol, 80 g (2 moles) de soude, 60 g d'eau et 1 250 g (11 moles) de chlorobenzène. On chauffe alors jusqu'à 133 °C tandis que l'eau est entraînée par azéotropie. La bouillie de crésolate de soude est fluide à 135 °C. A ce moment, on met un courant de gaz inerte (azote) et on charge 18 g (0,18 mole) de chlorure cuivreux et 38 g (0,104 mole) de tris(dioxa-3,6 octyl)amine. On maintient au reflux pendant 6 h tandis que l'avancement de la réaction est suivi par chromatographie en vérifiant la disparition du chlorobenzène et l'apparition du phénoxytoluène. Après 6 h à 135 °C, le taux de transformation est de 89 % et le rendement de 97 %.216 g (2 moles) of metacresol, 80 g (2 moles) are charged into a 2 I three-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a fraction separator. soda, 60 g of water and 1250 g (11 moles) of chlorobenzene. Then heated to 133 ° C while the water is entrained by azeotropy. The soda cresolate slurry is fluid at 135 ° C. At this time, an inert gas stream (nitrogen) is put on and 18 g (0.18 mole) of cuprous chloride and 38 g (0.104 mole) of tris (3.6-dioxa octyl) amine are charged. It is maintained at reflux for 6 h while the progress of the reaction is followed by chromatography, checking the disappearance of the chlorobenzene and the appearance of the phenoxytoluene. After 6 h at 135 ° C, the conversion rate is 89% and the yield 97%.
Après refroidissement, le chlorure de sodium est extrait à l'eau acide, puis à l'eau alcaline et la masse organique est soumise à distillation pour obtenir 302 g de métaphénoxytoluène PEbs: 120 °C d2°4: 1,045.After cooling, the sodium chloride is extracted with acid water, then with alkaline water and the organic mass is subjected to distillation to obtain 302 g of metaphenoxytoluene PEbs: 120 ° C d2 ° 4: 1.045.
Dans le même appareillage que ci-dessus, on charge 216 g (2 moles) de métacrésol, 60 g (1,5 moles) de soude, 28 g (0,5 mole) de potasse, 60 g d'eau et 1 250 g (11 moles) de chlorobene. On opère la salification comme dans l'exemple 1a puis après avoir mis la masse sous un courant d'hydrogène, on ajoute 17 g (0,17 mole) de chlorure cuivreux et 30 g (0,093 mole) de tris(dioxa-3,6 héptyl)amine. On maintient au reflux pendant 6 h tout en suivant l'avancement de la réaction. Après ce laps de temps, le taux de transformation du crésol atteint 90 % et le rendement 97 %.In the same apparatus as above was charged with 216 g (2 moles) of m-cresol, 60 g (1, 5 moles) of sodium hydroxide, 28 g (0.5 mol) of potassium hydroxide, 60 g of water and 1250 g (11 moles) of chlorobene. Salification is carried out as in Example 1a, then after having put the mass under a stream of hydrogen, 17 g (0.17 mole) of cuprous chloride and 30 g (0.093 mole) of tris (dioxa-3) are added, 6 heptyl) amine. Aintains m is refluxed for 6 hours while following the progress of the reaction. After this time, the cresol transformation rate reaches 90% and the yield 97%.
On opère comme ci-dessus mais sans ajouter d'agent séquestrant selon l'invention. Après 6 h, le degré d'avancement de la réaction n'est que 5 % et il faut attendre 106 h de reflux pour obtenir un taux de transformation de 50 %.The procedure is as above but without adding a sequestering agent according to the invention. After 6 h, the degree of progress of the reaction is only 5% and it is necessary to wait 106 h of reflux to obtain a conversion rate of 50%.
Préparation de métaphénoxytoluène
Dans un erlen de 100 cm3 agité par un barreau magnétique sous couverture d'azote, on charge 1,16 g (0,01 mole) de phénate de sodium, 20 g (0,158 mole) de chloro-3 toluène, 0,099 g (0,001 mole) de chlorure cuivreux et 0,36 g (0,001 mole) de tris(dioxa-3,6 octyl)amine. Après 4 h de reflux, le taux de transformation atteint 91 %.In an Erlenmeyer flask of 100 cm 3 stirred by a magnetic stirrer under nitrogen blanket was charged with 1.16 g (0.01 mole) of sodium phenoxide, 20 g (0.158 mol) of 3-chloro toluene, 0.099 g ( 0.001 mole) of cuprous chloride and 0.36 g (0.001 mole) of tris (dioxa-3,6 octyl) amine. After 4 hours of reflux, the transformation rate reaches 91%.
On opère comme ci-dessus mais sans ajouter de tris(dioxa-3,6 octyl)amine. Après 4 h de reflux le taux de transformation atteint 0,6 %.The procedure is as above but without adding tris (dioxa-3,6 octyl) amine. After 4 hours of reflux, the conversion rate reaches 0.6%.
Préparation de l'orthophénoxy toluène
Dans un erlen de 100 cm3 agité par un barreau magnétique, on charge 1,30 g (0,01 mole) d'orthocrésolate de sodium, 20 g (0,18 mole) de chlorobenzène, 0,099 g (0,001 mole) de chlorure cuivreux et 0,36 g (0,001 mole) de tris(dioxa-3,6 octyl)amine. Après 6 h de reflux, le taux de transformation atteint 92 %.1.30 g (0.01 mole) of sodium ortho-cresolate, 20 g (0.18 mole) of chlorobenzene, 0.099 g (0.001 mole) of chloride are charged into a 100 cm 3 Erlenmeyer flask stirred with a magnetic bar. copper and 0.36 g (0.001 mole) of tris (dioxa-3.6 octyl) amine. After 6 h of reflux, the transformation rate reaches 92%.
Le même essai est réalisé sans addition de tris(dioxa-3,6 octyl)amine. Après 6 h de reflux, le taux de transformation n'est que de 1,2%.The same test is carried out without the addition of tris (dioxa-3,6 octyl) amine. After 6 h of reflux, the conversion rate is only 1.2%.
Préparation du diphénoxy-1,2 benzène
Dans un erlen de 100 ml agité par un barreau magnétique on charge 2,32 g (0,002 mole) de phénate de sodium 1,47 g (0,01 mole) d'o-dichlorobenzène, 0,2 g (0,002 mole) de chlorure cuivreux et 0,72 g (0,002 mole) de tris(dioxa-3,6 octyl)amine dans 20 g d'anisole. Après 20 h au reflux, le taux de transformation est de 60 % en diphénoxy-1,2 benzène et de 5 % en chloro-1 phénoxy-2 benzène.2.32 g (0.002 mole) of sodium phenate 1.47 g (0.01 mole) of o-dichlorobenzene, 0.2 g (0.002 mole) are charged into a 100 ml Erlenmeyer flask stirred with a magnetic bar. copper chloride and 0.72 g (0.002 mole) of tris (dioxa-3.6 octyl) amine in 20 g of anisole. After 20 h at reflux, the conversion rate is 60% into 1,2-diphenoxy-benzene and 5% into 1-chloro-2-phenoxy-benzene.
Le même essai est réalisé sans ajouter de tris(dioxa-3,6 octyl)amine : le taux de transformation est nul après 20 h au reflux de l'anisole.The same test is carried out without adding tris (dioxa-3,6 octyl) amine: the conversion rate is zero after 20 h at reflux of the anisole.
Préparation de méthyl-3' phénoxy-2 fluorobenzène
Dans un erlen de 100 ml agité par un barreau magnétique et sous courant d'hydrogene, on charge 20 g (0,15 mole) de chloro-1 fluoro-2 benzène, 1,37 g (0,01 mole) de m-crésolate de sodium, 0,099 g (0,001 mole) de chlorure de cuivre et 0,36 g (0,001 mole) de tris(dioxa-3,6 octyl)amine. On chauffe à reflux pendant 24 h. Le taux de transformation en fluoro-1 méthyl-3' phénoxy-2 benzène atteint 75 %.20 g (0.15 mole) of 1-chloro-2 fluoro benzene, 1.37 g (0.01 mole) of m- are charged into a 100 ml Erlenmeyer flask stirred by a magnetic bar and under a stream of hydrogen. sodium cresolate, 0.099 g (0.001 mole) of copper chloride and 0.36 g (0.001 mole) of tris (3.6-dioxa-octyl) amine. The mixture is heated at reflux for 24 h. The conversion rate into fluoro-1 methyl-3 'phenoxy-2 benzene reaches 75%.
On opère comme ci-dessus mais sans ajouter de tris(dioxa-3,6 octyl)amine. Le taux de transformation est de 11 % après 24 h de reflux.The procedure is as above but without adding tris (dioxa-3,6 octyl) amine. The conversion rate is 11% after 24 h of reflux.
Préparation de fluoro-3' phénoxy-3 toluène
Dans un ballon de 500 ml équipé d'une agitation et chauffé par bain d'huile, on charge 110 g (0.87 mole) de chloro-3 toluène, 8 g (0,06 mole) de métafluorophénate de sodium, 0,6 g (0,006 mole) de chlorure cuivreux et 2,2 g (0,006 mole) de tris(dioxa-3,6 octyl)amine. On chauffe 8 h 30 à reflux (180 °C). Le taux de conversion en m-fluoro-3'phénoxytoluène atteint alors 65,9 %.110 g (0.87 mole) of 3-chloro toluene, 8 g (0.06 mole) of sodium metafluorophenate, 0.6 g are charged into a 500 ml flask equipped with stirring and heated in an oil bath. (0.006 mole) of cuprous chloride and 2.2 g (0.006 mole) of tris (dioxa-3,6 octyl) amine. It is heated 8:30 at reflux (180 ° C). The conversion rate to m-fluoro-3'phenoxytoluene then reaches 65.9%.
On opère comme ci-dessus mais sans ajouter d'agent séquestrant : le taux de transformation est de 5%.The procedure is as above but without adding a sequestering agent: the transformation rate is 5%.
Préparation de métaphénoxybenzonitrile
Dans un ballon de 1 I, équipé comme dans l'exemple 1, on charge 100 g (0,73 mole) de chloro-3 benzonitrile, 98 g (0,84 mole) de phénate de sodium, 7,2 g (0,072 mole) de chlorure cuivreux, 10,3 g (0,028 mole) de tris(dioxa-3,6 octyl)amine et 570 g d'anisole. On chauffe alors à reflux (155 °C) sous atmosphère d'azote pendant 6 h. Le taux de transformation est de 85 % et le rendement en m-phénoxybenzonitrile distillé est de 70 %.100 g (0.73 mole) of 3-chloro-benzonitrile, 98 g (0.84 mole) of sodium phenate, 7.2 g (0.072) are loaded into a 1 I flask equipped as in Example 1 mole) of cuprous chloride, 10.3 g (0.028 mole) of tris (3,6-dioxa octyl) amine and 570 g of anisole. Then heated to reflux (155 ° C) under nitrogen for 6 h. The conversion rate is 85% and the yield of distilled m-phenoxybenzonitrile is 70%.
On opère comme sous a) en remplaçant l'anisole par l'oxyde de phényle qui permet de chauffer à 180 °C pendant 6 h. Le taux de transformation est alors de 95 % et le rendement en m-phénoxybenzonitrile distillé, de 70 %.The procedure is as under a), replacing the anisole with phenyl oxide which allows heating at 180 ° C for 6 h. The conversion rate is then 95% and the yield of distilled m-phenoxybenzonitrile, 70%.
On opère comme sous b) sans ajouter de tris(dioxa-3,6 octyl)amine. Le taux de transformation après 6 h est de 15 %.The procedure is as in b) without adding tris (dioxa-3,6 octyl) amine. The transformation rate after 6 h is 15%.
Préparation de métaphénoxybenzonitrile
Dans un ballon de 3 1 équipé comme dans l'exemple 1, on charge 192 g (3,43 moles) de potasse, 252 g d'eau, 320 g (3,8 moles) de phénol et 675 g d'anisole. On opère la salification en chauffant à reflux pour éliminer l'eau par azéotropie. On met ensuite l'appareillage sous azote et on charge 460 g (3,34 moles) de chlorobenzonitrile dissous dans 500 g d'anisole, 36 g (0,36 mole) de chlorure cuivreux et 26 g (0,057 mole) de tris(trioxa-3,6,9 décyl)amine. On maintient au reflux (140 °C) pendant 6 h : le taux de conversion atteint 80 %.192 g (3.43 moles) of potassium hydroxide, 252 g of water, 320 g (3.8 moles) of phenol and 675 g of anisole are charged into a 3 1 flask equipped as in Example 1. Salification is carried out by heating at reflux to remove the water by azeotropy. The apparatus is then placed under nitrogen and 460 g (3.34 moles) of chlorobenzonitrile dissolved in 500 g of anisole, 36 g (0.36 mole) of cuprous chloride and 26 g (0.057 mole) of tris are charged. trioxa-3,6,9 decyl) amine. Is maintained at reflux (140 ° C) for 6 h: the conversion rate reaches 80%.
Après refroidissement de la masse, on extrait les chlorures par de l'eau acidulée et après décantation de la couche aqueuse, on récupère par distillation l'anisole, le phénol non réagi et le m-phénoxybenzonitrile. PEb0,5 : 127 °C - Rendement : 73 %.After cooling the mass, the chlorides are extracted with acidulated water and after decantation of the aqueous layer, the anisole, unreacted phenol and m-phenoxybenzonitrile are recovered by distillation. PEb 0.5 : 127 ° C - Yield: 73%.
Préparation du métaphénoxynitrobenzène
Dans un erlen de 100 cm3 agité par un barreau magnétique sous atmosphère d'azote, on charge 7,9 g (0,05 mole) de m-chloronitrobenzène, 5,8 g (0,05 mole) de phénate de sodium, 0,5 g (0,005 mole) de chlorure cuivreux, 1,85 g (0,005 mole) de tris(dioxa-3,6 octyl)amine dans 50 cm3 d'anisole. On chauffe à reflux pendant 6 h. Le taux de conversion atteint alors 72 %.7.9 g (0.05 mole) of m-chloronitrobenzene, 5.8 g (0.05 mole) of sodium phenate are charged into a 100 cm 3 Erlenmeyer flask stirred by a magnetic bar under a nitrogen atmosphere. 0.5 g (0.005 mole) of cuprous chloride, 1.85 g (0.005 mole) of tris (dioxa-3,6 octyl) amine in 50 cm 3 of anisole. The mixture is heated at reflux for 6 h. The conversion rate then reaches 72%.
Le taux de transformation n'atteint que 12 % si on opère sans ajouter la tris(dioxa-3,6 octyl)amine.The transformation rate only reaches 12% if one operates without adding the tris (dioxa-3,6 octyl) amine.
Préparation du métaphénoxybenzoate de méthyle.
Dans un ballon de 1 I équipé comme dans l'exemple 1, on charge 17,1 g (0,098 mole) de métachlorobenzoate de méthyle, 11,6 g (0,1 mole) de phénate de sodium, 1 g (0,001 mole) de chlorure cuivreux et 3,7 g (0,001 mole) de tris(dioxa-3,6 octyl)amine dans 300 g d'anisole. Après 6 h au reflux, le taux de transformation est de 75 %.17.1 g (0.098 mole) of methyl metachlorobenzoate, 11.6 g (0.1 mole) of sodium phenate, 1 g (0.001 mole) are loaded into a 1 I flask equipped as in Example 1 of cuprous chloride and 3.7 g (0.001 mole) of tris (dioxa-3.6 octyl) amine in 300 g of anisole. After 6 h at reflux, the conversion rate is 75%.
Le même essai conduit, sans tris(dioxa-3,6 octyl)amine ne permet qu'un taux de transformation de 1.5%.The same test conducted, without sorting (dioxa-3,6 octyl) amine only allows a conversion rate of 1.5%.
Préparation de méthyl-2'phénoxy-1 trifluorométhyl-4 benzène
Dans un ballon de 1 I équipé comme dans l'exemple 1, on charge 65 g (0,5 mole) de m-crésolate de sodium, 90,25 g (0,5 mole) de p-chlorotrifluorométhyl-benzène, 5 g (0,005 mole) de chlorure cuivreux, 18 g (0,056 mole) de tris(dioxa-3,6 heptyl)amine et 300 g d'anisole. Après 6 h de reflux à 150 °C, le taux de transformation atteint 75 %.65 g (0.5 mole) of sodium m-cresolate, 90.25 g (0.5 mole) of p-chlorotrifluoromethyl-benzene, 5 g are loaded into a 1 I flask equipped as in Example 1 (0.005 mole) of cuprous chloride, 18 g (0.056 mole) of tris (3,6-dioxa heptyl) amine and 300 g of anisole. After 6 h of reflux at 150 ° C, the conversion rate reaches 75%.
Sans tris(dioxa-3,6 heptyl)amine, le taux de transformation n'est, après 6 h, que de 3,4 %.Without tris (3,6-heptyl) amine, the conversion rate is, after 6 h, than 3, 4%.
Préparation de métaphénoxytoluène
Dans un appareil en acier inox de 100 1 équipé d'une colonne à distiller, on charge 14,3 kg (132,4 moles) de m-crésol, 75 kg (667 moles) de chlorobenzène, 9,24 kg de soude 36° Bé, 4,48 kg de potasse 50 %. On opère la salification en distillant l'eau par azéotropie. Dès que la température de la masse atteint 132 °C, on charge 1,6 kg (16 moles) de chlorure cuivreux, 2 kg (5,5 moles) de tris(dioxa-3,6 octyl)amine et on fait passer un courant d'hydrogène. Après 5 h de reflux à 135 °C, le taux de conversion atteint 88% et le rendement 93 %.14.3 kg (132.4 moles) of m- cresol, 75 kg ( 667 moles) of chlorobenzene, 9.24 kg of sodium hydroxide are charged into a 100 l stainless steel apparatus equipped with a distillation column. 36 ° Be, 4.48 kg of 50% potash. Salification is carried out by distilling the water by azeotropy. As soon as the temperature of the mass reaches 132.degree . C., 1.6 kg (16 moles) of cuprous chloride, 2 kg (5.5 moles) of tris (dioxa-3.6 octyl) amine are loaded and passed through. a stream of hydrogen. After 5 h of reflux at 135 ° C., the conversion rate reaches 88% and the yield 93%.
Après refroidissement à 80 °C, on extrait les sels formés à l'eau acide puis on soumet la masse organique à une distillation pour éliminer l'excès de chlorobenzène, le crésol non réagi, puis le m- phénoxytoluène. On obtient ainsi 21,6 kg de m-phénoxytoluène, soit un rendement de 89 %.After cooling to 80 ° C., the salts formed are extracted with acidic water and then the organic mass is subjected to a distillation in order to remove the excess of chlorobenzene, the unreacted cresol, then the m - phenoxytoluene. Thereby obtaining 21.6 kg of m-phenoxytoluene, or a yield of 8 9%.
Dans un erlenmeyer de 100 cm3, agité par un barreau magnétique sous atmosphère d'azote, on charge 2,88 g du sel de sodium formé à partir du méta-hydroxy benzaldéhyde soit 0,02 mole, 60 g de bromobenzène, 0,2 g de Cu CI (0,002 mole) et 0,15 g de tris(dioxa-3,6 octyl)amine. Le mélange est chauffé à 150 °C pendant 8 h. Le rendement de la réaction en méta-phénoxy-benzaldéhyde est de 75%.2.88 g of the sodium salt formed from meta-hydroxy benzaldehyde, ie 0.02 mole, 60 g of bromobenzene, 0, are charged into a 100 cm 3 Erlenmeyer flask, stirred by a magnetic bar under a nitrogen atmosphere. 2 g of Cu CI (0.002 mole) and 0.15 g of tris (dioxa-3.6 octyl) amine. The mixture is heated at 150 ° C for 8 h. The yield of the meta-phenoxy-benzaldehyde reaction is 75%.
Le taux de transformation en méta-phénoxy-benzaldéhyde n'atteint que 1 % si on opère sans ajouter la tris(dioxa-3,6 octyl)amine.The conversion rate into meta-phenoxy-benzaldehyde only reaches 1% if one operates without adding the tris (dioxa-3,6 octyl) amine.
Préparation de la tris(dioxa-3,6 octyl)amine.
- a) Dans un ballon tricol de 1 I, muni d'un agitateur mécanique, d'un thermomètre, d'un réfrigérant, on introduit 450 g d'éthoxy-2 éthanol (5 moles). On ajoute 23 g de sodium (1 mole), en 3 h en maintenant la température de mélange à 40 °C.
- b) Au mélange précédent, on ajoute 51,6 g de chlorhydrate de tris(chloro-2 éthyl)amine (soit 0,215 mole). On chauffe alors le mélange à reflux pendant 12 h puis on distille le solvant sous pression réduite. Le ethoxy-2 ethanolate de sodium en excès est neutralisé par addition de 12 cm3 d'H CI aqueux (10 N). Le chlorure de sodium est filtré et la solution est distillée. La tris(dioxa-3,6 octyl)amine distille entre 200 °C et 210 °C sous 1 mmHg. Le rendement est de 68 %.
- a) 450 g of 2-ethoxy-ethanol (5 moles) are introduced into a 1 I three-necked flask fitted with a mechanical stirrer, a thermometer and a condenser. 23 g of sodium (1 mol) are added over 3 hours while maintaining the mixing temperature at 40 ° C.
- b) To the preceding mixture, 51.6 g of tris (2-chloroethyl) amine hydrochloride (ie 0.215 mole) are added. The mixture is then heated at reflux for 12 h and then the solvent is distilled under reduced pressure. The excess sodium ethoxy-2 ethanolate is neutralized by the addition of 12 cm 3 of aqueous HCl (10 N). The sodium chloride is filtered and the solution is distilled. The tris (dioxa-3,6 octyl) amine distills between 200 ° C and 210 ° C under 1 mmHg. The yield is 68%.
Préparation de la tris(dioxa-3,6 heptyl)amine.
- a) Dans un ballon tricol de 1 I, muni d'un agitateur mécanique, d'un thermomètre, d'un réfrigérant, on introduit 380 g de méthoxy-2 éthanol (5 moles). On ajoute 23 g de sodium (1 mole) en 3 h en maintenant la température de mélange à 40 °C.
- b) au mélange précédent, on ajoute 51,6 g de chlorhydrate de tris(chloro-2 éthyl)amine (soit 0,215 mole). On chauffe alors le mélange à reflux (125 °C) pendant 12 h, puis on distille le solvant sous pression réduite. Le méthoxy-2 éthanolate de sodium en excès est neutralisé par addition de 11,6 cm3 d'HCI aqueux (10 N). Le chlorure de sodium est filtré et la solution est distillée.
- a) 380 g of methoxy-2 ethanol (5 moles) are introduced into a 1 I three-necked flask fitted with a mechanical stirrer, a thermometer and a condenser. 23 g of sodium (1 mol) are added over 3 h while maintaining the mixing temperature at 40 ° C.
- b) to the preceding mixture, 51.6 g of tris (2-chloroethyl) amine hydrochloride (ie 0.215 mole) are added. The mixture is then heated to reflux (125 ° C) for 12 h, then the solvent is distilled under reduced pressure. The excess sodium methoxy-2 ethanolate is neutralized by the addition of 11.6 cm 3 of aqueous HCl (10 N). The sodium chloride is filtered and the solution is distilled.
Préparation de la tris(trioxa-3,6,9 decyl)amine.Preparation of the tris (trioxa-3,6,9 decyl) amine.
Dans un ballon tricol de 1 1 équipé d'un agitateur mécanique, d'un condenseur et d'un thermomètre, on introduit 600 g d'éther monométhylique du diéthylène glycol (dioxa-3,6 heptanol-1) soit 5 moles puis 23 g de sodium (1 mole) par petites fractions afin de former le dioxa-3,6 heptanolate de sodium.In a 1 1 three-necked flask equipped with a mechanical stirrer, a condenser and a thermometer, 600 g of diethyl glycol monomethyl ether (3.6-dioxa heptanol-1) are introduced, ie 5 moles then 23 g of sodium (1 mole) in small fractions to form the dioxa-3,6 sodium heptanolate.
Lorsque le sodium est totalement transformé, on ajoute alors 51,8 g de chlorhydrate de la tris(chloro-2 éthyl)amine (soit 0,215 mole). Le mélange est chauffé à 130 °C pendant 8 h sous agitation puis refroidi et l'excès d'alcoolate de sodium neutralisé par une solution aqueuse d'acide chlorhydrique à 10 %. Le dioxa-3,6 heptanol-1 est éliminé par distillation à 130 °C sous 20 mmHg. Le mélange obtenu est filtré afin d'éliminer le chlorure de sodium puis le produit est distillé. On obtient ainsi 83 g de tris(trioxa-3,6,9 décyl)amine qui distille à 189 °C sous 0,1 mmHg.When the sodium is completely transformed, 51.8 g of tris (2-chloroethyl) amine hydrochloride (i.e. 0.215 mole) are then added. The mixture is heated at 130 ° C. for 8 h with stirring then cooled and the excess sodium alcoholate neutralized with a 10% aqueous hydrochloric acid solution. The dioxa-3,6 heptanol-1 is removed by distillation at 130 ° C under 20 mmHg. The mixture obtained is filtered in order to remove the sodium chloride and then the product is distilled. 83 g of tris (trioxa-3,6,9 decyl) amine are thus obtained which distills at 189 ° C under 0.1 mmHg.
Claims (18)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT80400595T ATE486T1 (en) | 1979-05-18 | 1980-04-30 | PROCESS FOR THE PREPARATION OF DIARYL ETHERS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7912688A FR2456727A1 (en) | 1979-05-18 | 1979-05-18 | PROCESS FOR THE PREPARATION OF DIARYL ETHERS |
| FR7912688 | 1979-05-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0021868A1 EP0021868A1 (en) | 1981-01-07 |
| EP0021868B1 true EP0021868B1 (en) | 1981-12-23 |
Family
ID=9225628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80400595A Expired EP0021868B1 (en) | 1979-05-18 | 1980-04-30 | Process for the preparation of diaryl ethers |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4288386A (en) |
| EP (1) | EP0021868B1 (en) |
| JP (1) | JPS5857412B2 (en) |
| AT (1) | ATE486T1 (en) |
| AU (1) | AU536597B2 (en) |
| BR (1) | BR8003044A (en) |
| CA (1) | CA1124741A (en) |
| DE (1) | DE3060113D1 (en) |
| ES (1) | ES8200634A1 (en) |
| FI (1) | FI72312C (en) |
| FR (1) | FR2456727A1 (en) |
| PL (1) | PL128067B1 (en) |
| ZA (1) | ZA802937B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3118371A1 (en) * | 1981-05-09 | 1982-11-25 | Bayer Ag, 5090 Leverkusen | SUBSTITUTED PHENOXYBENZALDEHYDE ACETALS, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF AS HERBICIDES AND PLANT GROWTH REGULATORS |
| US4612400A (en) * | 1985-02-14 | 1986-09-16 | The Dow Chemical Company | Autoxidation of bis(ortho dialkyl-phenoxy)benzophenones |
| US5283371A (en) * | 1986-03-13 | 1994-02-01 | National Research Development Corporation | Intermediates useful in the production of pesticides |
| GB8614002D0 (en) * | 1986-06-09 | 1986-07-16 | Ici Plc | Halogenated diphenyl ether derivatives |
| US4766253A (en) * | 1987-05-04 | 1988-08-23 | Ciba-Geigy Corporation | Process for preparing chlorinated diphenyl ethers |
| US4948904A (en) * | 1988-12-14 | 1990-08-14 | Occidental Chemical Corporation | Process for the preparation of oxydiphthalic anhydrides |
| US4946985A (en) * | 1988-12-14 | 1990-08-07 | Occidental Chemical Corporation | Catalyzed process for the preparation of oxydiphthalic anhydrides |
| US4982010A (en) * | 1989-10-31 | 1991-01-01 | Yoshitomi Pharmaceutical Industries, Ltd. | Method of producing 4-biphenyl p-tolyl ether |
| JP3233678B2 (en) * | 1991-06-27 | 2001-11-26 | 日本化学工業株式会社 | Method for producing o-alkoxybenzoic acid |
| US5235020A (en) * | 1991-12-31 | 1993-08-10 | Amoco Corporation | Process for preparation of poly(aryl ether) polymers by acyclic catalysts |
| WO1999018057A1 (en) | 1997-10-06 | 1999-04-15 | Massachusetts Institute Of Technology | Preparation of diaryl ether by condensation reactions |
| CN101885670A (en) * | 2010-07-19 | 2010-11-17 | 扬州大学 | Synthesis method of m-phenoxytoluene |
| CN102321380A (en) * | 2011-06-22 | 2012-01-18 | 南通市争妍颜料化工有限公司 | Method for preparing high-hiding variety paratonere 2BL of paratonere 177 |
| CN103342630B (en) * | 2013-07-30 | 2015-01-21 | 黑龙江大学 | Method for synthesizing diaryl ether compounds |
| CN112661624B (en) * | 2020-12-30 | 2022-09-02 | 锦州三丰科技有限公司 | Preparation method of m-phenoxy benzaldehyde |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3083234A (en) * | 1963-03-26 | Process fos preparing bib |
-
1979
- 1979-05-18 FR FR7912688A patent/FR2456727A1/en active Granted
-
1980
- 1980-04-30 AT AT80400595T patent/ATE486T1/en not_active IP Right Cessation
- 1980-04-30 EP EP80400595A patent/EP0021868B1/en not_active Expired
- 1980-04-30 DE DE8080400595T patent/DE3060113D1/en not_active Expired
- 1980-05-12 US US06/148,590 patent/US4288386A/en not_active Expired - Lifetime
- 1980-05-16 ZA ZA00802937A patent/ZA802937B/en unknown
- 1980-05-16 ES ES491541A patent/ES8200634A1/en not_active Expired
- 1980-05-16 FI FI801599A patent/FI72312C/en not_active IP Right Cessation
- 1980-05-16 AU AU58458/80A patent/AU536597B2/en not_active Ceased
- 1980-05-16 JP JP55064135A patent/JPS5857412B2/en not_active Expired
- 1980-05-16 CA CA352,089A patent/CA1124741A/en not_active Expired
- 1980-05-16 BR BR8003044A patent/BR8003044A/en unknown
- 1980-05-17 PL PL1980224312A patent/PL128067B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA1124741A (en) | 1982-06-01 |
| FR2456727B1 (en) | 1981-07-03 |
| FI801599A (en) | 1980-11-19 |
| ES491541A0 (en) | 1981-11-01 |
| ZA802937B (en) | 1981-06-24 |
| JPS5629539A (en) | 1981-03-24 |
| ES8200634A1 (en) | 1981-11-01 |
| EP0021868A1 (en) | 1981-01-07 |
| FI72312C (en) | 1987-05-11 |
| PL224312A1 (en) | 1981-02-13 |
| US4288386A (en) | 1981-09-08 |
| FR2456727A1 (en) | 1980-12-12 |
| PL128067B1 (en) | 1983-12-31 |
| ATE486T1 (en) | 1982-01-15 |
| JPS5857412B2 (en) | 1983-12-20 |
| AU536597B2 (en) | 1984-05-17 |
| FI72312B (en) | 1987-01-30 |
| DE3060113D1 (en) | 1982-02-11 |
| BR8003044A (en) | 1980-12-23 |
| AU5845880A (en) | 1980-11-20 |
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